一氧化碳分子在鉛、銅修飾的鉑(111)電極上氧化及還原現象

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黃建瑋(Jian-Wei Huang) 查詢紙本館藏

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化學學系

論文名稱

一氧化碳分子在鉛、銅修飾的鉑(111)電極上氧化及還原現象

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摘要(中)

本論文利用循環伏安法(Cyclic Voltammetry，CV)和掃描式電子穿隧顯微鏡(Scanning Tunneling Microscope，STM)，探討在鉛修飾於Pt(111)電極上的結構及對於一氧化碳吸附和氧化的影響，另一部分為銅沉積於Pt(111)電極上於氫氧化鉀中形貌的變化及吸附和還原一氧化碳的過程。
經過鉛修飾後一氧化碳的氧化電位提前60 mV，由STM結果得知鉛沉積的過程中首先會無序的吸附於Pt(111)電極上，隨著電位往負移動至-50 mV(vs. Ag/AgCl)產生覆蓋度為0.54的(7  57)結構，持續將電位往負移動至-250 mV產生(3  23) 覆蓋度為0.67及(21  21) 覆蓋度為0.59兩種不同的有序結構。
加入一氧化碳後會破壞鉛薄膜，原先的鉛原子會被一氧化碳分子取代產生(2  2) 覆蓋度為0.75的吸附結構，隨著一氧化碳分子離開STM容槽，溶液中的鉛離子會重新吸附回Pt(111)電極與一氧化碳形成混合均勻的(3  7 ) 共吸附結構，鉛及一氧化碳覆蓋度均為0.22。此共吸附結構在電位往正移動時於缺陷處及相鄰有序吸附層間會開始出現氫氧根的吸附，因此斷定此為一氧化碳分子發生氧化的活性位點。
沉積於Pt(111)電極上的銅膜在氫氧化鉀中移至-500 mV時會開始發生氧化，由旋轉電極可以測得銅膜在氧化的過程中會有溶解的現象，並且將電位往負移動至-800 mV後原先破碎的銅氧化物會還原為平整的金屬銅表面，證明銅薄膜在氫氧化鉀中的氧化還原過程具有可逆性，於-700 mV加入一氧化碳後觀察到氫氧根與一氧化碳共吸附的有序結構，該結構於-1 V時消失並且臺階邊緣出現許多亮點，可能為一氧化碳即將被還原的現象。

摘要(英)

In this study, cyclic voltammetry (CV) and scanning tunneling microscope (STM) were used to explore the adsorption and oxidation of carbon monoxide (CO) on Lead-modified Pt(111) electrode. The electrified interface of a copper film supported by Pt(111) electrode in potassium hydroxide was also examined. The adsorption and reduction of carbon monoxide at this Cu film was revealed by in situ STM.
After being modified by lead, the oxidation potential of carbon monoxide is shifted positively by 60 mV. STM results showed that lead was first adsorbed on the Pt(111) electrode in disorder in the first stage of deposition, yielding a (7  57) structure with a coverage of 0.54 at -50 mV (vs. Ag/AgCl). Shifting the potential negatively to -250 mV produced two different ordered structures, (3  23) and (21  21) with a coverage of 0.67 and 0.59.
The addition of CO into the cell displaced the lead film at 0 V, leading to the renowned (2  2) – CO structure (coverage = 0.75). As the solution CO escaped from the STM cell, lead ions in the solution were adsorbed back to the Pt(111) electrode. STM imaging yielded a well ordered (3  7 ) structure, ascribed to homogeneously coadsorbed CO and Pb, whose coverages were both 0.22. As the potential was stepped to positive potential, aggregated features appeared the perimeters of mixed ordered domains, showing these sites were more active than the terrace site toward the oxidation of CO.
In KOH the Pt(111) – supported Cu film started to oxidize at E > -500 mV (vs. Ag/AgCl). The rotating disk ring electrode was used to reveal that the copper film dissolved during the oxidation process, along with the formation of a rough oxide film. After switching the potential negative to -800 mV, copper oxide were reduced to expose a flat metallic copper surface. This kinetics of this reduction process was revealed by the in situ STM.
After adding CO into the STM cell at -700 mV, an ordered (7  7) structure was imaged, which is ascribed to coadsorbed hydroxide and CO. This structure disappeared at -1 V and brighter rings appeared at the upper edge of the step, which is ascribed to CO reduction process. STM imaging revealed CO molecules were adsorbed on fcc and hcp sites on the Cu film having a Cu(111) texture. The two types of CO admolecules exhibited different corrugation heights.

關鍵字(中)

★ 鉛
★ 銅
★ 一氧化碳氧化反應
★ 一氧化碳還原反應

關鍵字(英)

★ lead
★ copper
★ carbon monoxide oxidation reaction
★ carbon monoxide reduction reaction

論文目次

摘要 I
Abstract II
致謝 IV
目錄 V
圖目錄 IX
表目錄 XIV
第一章、緒論 1
1-1 燃料電池介紹 1
1-1-1燃料電池的原理 1
1-1-2一氧化碳吸附於鉑的現象 1
1-1-3一氧化碳分子於鉑氧化的反應 2
1-2鉛 2
1-2-1親氧性 2
1-2-2於工業上的應用 2
1-2-3甘油的氧化 3
1-3一氧化碳還原 3
1-3-1二氧化碳還原 3
第二章、實驗步驟 6
2-1 藥品部分 6
2-2 實驗用氣體 6
2-3 金屬線材 6
2-4 實驗用儀器 7
2-4-1 循環伏安儀（Cyclic Voltammetry , CV） 7
2-4-2 掃描式穿隧電子顯微鏡（Scanning Tunneling Microscope , STM） 7
2-4-3 點焊機(D.C. Spot Welder) 8
2-4-4 研磨拋光機（Grinder and Polisher） 8
2-4-5 超音波震盪器（Ultrasonic Cleaner） 8
2-5實驗步驟 11
2-5-1 鉑(111)單晶CV電極製備 11
2-5-2 鉑(111)單晶STM電極製備 11
2-5-3 STM探針製備 11
2-5-4 循環伏安法(CV)的實驗步驟 12
2-5-5 電化學掃描式穿隧電子顯微鏡(EC-STM)的實驗步驟 13
第三章、一氧化碳在過氯酸中於Pt(111)電極上的吸附現象 15
3-1 一氧化碳在過氯酸中於Pt(111)電極上的吸附現象 15
3-1-1 Pt(111)電極於過氯酸中之循環伏安圖 15
3-1-2一氧化碳吸附於Pt(111)電極在過氯酸中氧化之循環伏安圖 15
3-1-3一氧化碳吸附於Pt(111)電極在過氯酸中氧化之i-t curve圖 16
3-2 Pt(111)電極修飾鉛後於過氯酸中觀察一氧化碳吸附現象 21
3-2-1 於Pt(111)電沉積鉛在0.1 M過氯酸的循環伏安圖 21
3-2-2 於Pt(111)電沉積鉛在0.1 M過氯酸的STM圖 23
3-2-3 Pt(111)電極浸泡0.1 M過氯酸鉛不同時間在0.1 M過氯酸的循環伏安圖 32
3-2-4 Pt(111)電極浸泡0.1 M過氯酸鉛3 分鐘在0.1 M過氯酸的STM圖 32
3-2-5 於Pt(111)修飾鉛後在0.1 M過氯酸吸附一氧化碳的循環伏安圖 33
3-2-6 修飾鉛後在0.1 M過氯酸吸附一氧化碳氧化之i-t curve圖 34
3-2-7 於Pt(111)電沉積鉛後吸附一氧化碳在0.1 M過氯酸的STM圖 40
3-3 Pt(111)電極於硫酸中修飾鉛 48
3-3-1 Pt(111)電極於硫酸中之循環伏安圖 48
3-3-2 Pt(111)電極浸泡0.1 M過氯酸鉛不同時間在0.1 M硫酸的循環伏安圖 48
3-3-3 Pt(111)電極浸泡0.1 M過氯酸鉛1 分鐘在0.1 M硫酸的STM圖 49
3-4 Pt(111)電極修飾釕後於過氯酸中觀察一氧化碳吸附現象 49
3-4-1 於Pt(111)電沉積釕在0.1 M過氯酸的循環伏安圖 49
3-4-2 於Pt(111)修飾釕後在0.1 M過氯酸吸附一氧化碳的循環伏安圖 50
3-4-3 修飾鉛後在0.1 M過氯酸吸附一氧化碳氧化之i-t curve圖 51
3-5 Pt(111)修飾釕及鉛後吸附一氧化碳觀察甲酸氧化現象 57
3-5-1 Pt(111)電極在0.1 M過氯酸進行甲酸氧化之循環伏安圖 57
3-5-2 Pt(111)電極在0.1 M過氯酸吸附一氧化碳後進行甲酸氧化之循環伏安圖 57
3-5-3 Pt(111)電極修飾鉛在0.1 M過氯酸進行甲酸氧化之循環伏安圖 58
3-5-4 鉛修飾於Pt(111)電極在0.1 M過氯酸吸附一氧化碳後進行甲酸氧化之循環伏安圖 58
3-5-5 Pt(111)電極修飾釕在0.1 M過氯酸進行甲酸氧化之循環伏安圖 59
3-5-6 釕修飾於Pt(111)電極在0.1 M過氯酸吸附一氧化碳後進行甲酸氧化之循環伏安圖 60
第四章、探討銅沉積於Pt(111)電極上的效率以及其對於一氧化碳還原的催化活性 66
4-1 不同陰離子對銅沉積於Pt(111)電極上的效率 66
4-1-1 於Pt(111)電沉積銅在0.1 M硫酸的循環伏安圖 66
4-1-2 於Pt(111)電沉積銅在0.1 M硫酸的STM圖 66
4-1-3 於Pt(111)電沉積銅在0.1 M過氯酸的循環伏安圖 67
4-1-4 於Pt(111)電沉積銅在0.1 M過氯酸的STM圖 68
4-1-5 含氯離子溶液於Pt(111)電沉積銅在0.1 M硫酸的循環伏安圖 74
4-1-6含氯離子溶液於Pt(111)電沉積銅在0.1 M硫酸的STM圖 75
4-1-7 含溴離子溶液於Pt(111)電沉積銅在0.1 M硫酸的循環伏安圖 75
4-1-8含溴離子溶液於Pt(111)電沉積銅在0.1 M硫酸的STM圖 76
4-2 於Pt(111)電沉積銅後修飾鳥嘌呤觀察抗腐蝕效率 76
4-2-1 Pt(111)電極於0.1 M過氯酸電沉積銅後取出過水的循環伏安圖 77
4-2-2 Pt(111)電極於0.1 M過氯酸電沉積銅後修飾鳥嘌呤取出過水的循環伏安圖 77
4-2-3 Pt(111)電極於0.1 M過氯酸電沉積銅後修飾鳥嘌呤的STM圖 78
4-3 Pt(111)電極於0.1 M硫酸將銅及錫進行共沉積 88
4-3-1 Pt(111)電極於0.1 M硫酸電沉積錫的循環伏安圖 88
4-3-2 Pt(111)電極於0.1 M硫酸修飾錫後電沉積銅的循環伏安圖 89
4-3-3 Pt(111)電極於0.1 M硫酸電沉積銅後再沉積錫的STM圖 89
4-4 一氧化碳在Pt(111)電極沉積銅後於氫氧化鉀中的吸附現象 90
4-4-1 Pt(111)電極電沉積銅後於0.1 M氫氧化鉀的循環伏安圖 90
4-4-2 銅膜於0.1 M 氫氧化鉀中產生溶解現象的循環伏安圖 91
4-4-3 Pt(111)電極電沉積銅後於0.1 M氫氧化鉀的STM圖 92
4-4-4 Pt(111)電極電沉積銅後於0.1 M氫氧化鉀吸附一氧化碳的循環伏安圖 92
4-4-5 Pt多晶旋轉電極電沉積銅後於0.1 M氫氧化鉀還原一氧化碳的循環伏安圖 93
4-4-6 Pt(111)電極電沉積銅後於0.1 M氫氧化鉀吸附一氧化碳的STM圖 94
第五章、結論 113
第六章、參考文獻 114

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指導教授

姚學麟(Shueh-Lin Yau)

審核日期

2022-8-10

推文